Florfenicol (FLO) is a broad-spectrum halogenated antibiotic (containing F and Cl atoms), and the discharged FLO in wastewater exhibits potential biotoxicity. Peroxymonosulfate (PMS) activation can generate reactive oxygen species (ROSs) to realize efficient degradation of organic pollutants. Herein, Zn-substituted CoO (ZnCo) catalysts were prepared and applied in PMS activation for FLO degradation. The physicochemical properties were systematically studied by combining experiments and density functional theory (DFT) calculation. The Zn partial substitution induced electron rearrangement and promoted oxygen vacancy (OV) formation in CoO. ZnCo catalyst exhibited superior FLO removal, achieving a higher reaction rate of 0.112 min than CoO (0.053 min). The FLO degradation was highly dependent on the factors of PMS/ZnCo/FLO dosage, temperature, initial pH, and coexisting inorganic anions. The ZnCo also displayed outstanding performance in PMS activation for degradation of various typical organic pollutants. Electron paramagnetic resonance (EPR) spectra and quenching experiments indicated that both radical species (, , and ) and nonradical species (O) contribute to FLO removal. The redox cycle of Co/Co and OVs played an essential role in PMS activation. The electron structure of FLO and parameters of PMS adsorbed on ZnCo were calculated. The longer length of CoO and OO bonds for the adsorbed PMS could enhance its activation to generate ROSs. The intermediates were detected, and five degradation pathways were proposed. The acute and chronic toxicities of intermediates suggested that the dechlorination process is important for the toxicity attenuation of FLO. This study clarified the performance enhancement mechanism of Zn substitution on FLO degradation by PMS activation using CoO based catalyst, which favors the development of PMS-based advanced oxidation processes for wastewater treatment.

中文翻译：

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通过部分锌取代的 Co3O4 增强过一硫酸盐的活化来降解氟苯尼考：催化性能、降解机制和路线的见解


氟苯尼考（FLO）是一种广谱卤化抗生素（含有F和Cl原子），排放到废水中的FLO表现出潜在的生物毒性。过一硫酸盐（PMS）活化可产生活性氧（ROS），实现有机污染物的高效降解。本文制备了 Zn 取代的 CoO (ZnCo) 催化剂，并将其应用于 FLO 降解的 PMS 活化。通过实验和密度泛函理论（DFT）计算相结合，系统地研究了其理化性质。 Zn部分取代引起电子重排并促进CoO中氧空位（OV）的形成。 ZnCo 催化剂表现出优异的 FLO 去除率，反应速率比 CoO（0.053 分钟）更高，为 0.112 分钟。 FLO 的降解高度依赖于 PMS/ZnCo/FLO 剂量、温度、初始 pH 值和共存无机阴离子等因素。 ZnCo 在 PMS 活化降解各种典型有机污染物方面也表现出出色的性能。电子顺磁共振 (EPR) 谱和猝灭实验表明自由基物种 (、 和 ) 和非自由基物种 (O) 都有助于 FLO 的去除。 Co/Co 和 OV 的氧化还原循环在 PMS 激活中发挥着重要作用。计算了FLO的电子结构和ZnCo上吸附的PMS的参数。吸附的 PMS 的 CoO 和 OO 键长度较长，可以增强其活化作用，产生 ROS。检测到中间体，并提出了五种降解途径。中间体的急性和慢性毒性表明脱氯过程对于FLO的毒性衰减很重要。 本研究阐明了Zn取代对CoO基催化剂PMS活化降解FLO的性能增强机制，有利于基于PMS的废水处理高级氧化工艺的发展。